Search

The presence of anthropogenic nanoparticles (NPs) in the aquatic environment has become an emerging concern in terms of environmental and health safety. In the present study, we assessed the presence of Ag-bearing, Ti-bearing, and Ce-bearing NPs in the Barcelona catchment area, including the Besòs River basin and the Barcelona coast, and in the Ebro River Delta, using single particle inductively coupled plasma mass spectrometry (sp-ICP-MS). Ti-NPs and Ce-NPs were ubiquitously detected in surface waters, and their presence was related to a high natural background. Concentrations of Ti-NPs ranged from 23.2 × 10 to 298 × 10 Ti-NPs/L, with high concentrations being detected in areas with little anthropogenic pressure, while the presence of nanosilver (17.9 × 10 to 45.1 × 10 Ag-NPs/L) in the analyzed rivers was limited to certain hotspots close to wastewater treatment plants discharge points. The concentrations of Ce-NPs in the river ranged from 18.1 × 10 to 278 × 10 NPs/L, and they were related to the natural occurrence of the mineral Monazite-(Ce). Overall, the concentrations of these nanomaterials in the Barcelonan coast were significantly attenuated by river-sea environmental dilution. Nevertheless, Ce-NPs were eventually detected in some seawater samples with low levels of lanthanum-NPs, suggesting anthropogenic inputs of nanoCeO, probably from atmospheric deposition.

There is an increasing sense of alarm due to the constant accumulation of contaminants of emerging concern in the oceans. This fact was reflected in one of the significant challenges that are included in the United Nations Sustainable Development Goals which refer to climate change, conservation, and use of forests and oceans. Autonomous environmental monitoring techniques are required to set effective measures to conserve oceans. These detection systems are crucial tools for ambient data acquisition, remote monitoring, and mapping of the spatial extent of contaminants spills and plastic litter. Among the different technological operations that can be supported by these systems, the localisation of pollution sources has drawn increasing interest during recent years. This paper surveys recent advances in the new technologies for detection, mapping and new environmental monitoring strategies to detect marine contaminants of emerging concern and plastic litter.

Chemical stressors co-occur in mixtures into watercourses and this complicates predicting their effects on their ecological status. Our knowledge of river basin specific pollutants (RBSPs) is still limited, but it remains necessary to ensure the good chemical and ecological status. We performed an exercise on Mediterranean river sites exposed to urban and industrial pressures in order to, i) prioritize the occurring chemicals, ii) assessing the site's specific chemical risk (RQ), and iii) relating the chemical risk to the biological quality, using as evidences invertebrates and diatom indices. Mediterranean rivers suffer from strong pressures which lead to a poor dilution ability, which makes the inhabiting biota highly vulnerable. The most frequent pollutants in the 89 sites surveyed included pharmaceutical products such as the antibiotics azithromycin, clarithromycin, and erythromycin, and the anti-inflammatory diclofenac, and products of industrial origin such as perfluorinated PFOS, nickel, and nonylphenol. Both the diatom index IPS and the macroinvertebrate index IBMWP hold strong negative correlations to RQ, indicating a significant contribution of chemicals to biological impairment. Chemical contaminants (but not nutrients or dissolved organic carbon) were associated with significant changes to the taxonomic composition of invertebrate communities, but not to that of diatom communities. Our analyses indeed reveal that the impact of co-occurring chemicals translates onto negative effects in the biological quality. Our approach may be of use to evidence impacts on water resources and water quality in rivers under strong human pressure.

This study presents the application of a suspect screening approach to screen a wide range of natural toxins, including mycotoxins, bacterial toxins, and plant toxins, in surface waters. The method is based on a generic solid-phase extraction procedure, using three sorbent phases in two cartridges that are connected in series, hence covering a wide range of polarities, followed by liquid chromatography coupled to high-resolution mass spectrometry. The acquisition was performed in the full-scan and data-dependent modes while working under positive and negative ionisation conditions. This method was applied in order to assess the natural toxins in the Ter River water reservoirs, which are used to produce drinking water for Barcelona city (Spain). The study was carried out during a period of seven months, covering the expected prior, during, and post-peak blooming periods of the natural toxins. Fifty-three (53) compounds were tentatively identified, and nine of these were confirmed and quantified. Phytotoxins were identified as the most frequent group of natural toxins in the water, particularly the alkaloids group. Finally, the toxins identified to levels 2 and 1 were prioritised according to their bioaccumulation factor, biodegradability, frequency of detection, and toxicity. This screening and prioritisation approach resulted in different natural toxins that should be further assessed for their ecotoxicological effects and considered in future studies.

This study aimed to evaluate the presence of ultraviolet filters (UV-Fs), benzotriazoles, pyrethroids and per- and polyfluoroalkyl substances (PFASs) in freshwater and wastewater from the northern Antarctic Peninsula region. All water samples analyzed contained UV-Fs residues and high concentrations were detected in anthropogenic impacted sites (< LOD up to 1300 ng/L). Likewise, benzotriazoles were detected in all water samples (< LOQ–920 ng/L). Regarding suspended particulate matter, almost all UV-Fs and all benzotriazoles were measured at concentrations ranging from < LOQ to 33 µg/g dry weight. Pyrethroids were also detected (< LOQ–250 ng/L) and their presence implies the existence of a gateway to the Antarctica Peninsula from other regions. The data confirmed the presence of PFASs (< LOD–7500 ng/L) in this area, in agreement with previous studies. In light of these results, extended monitoring in Antarctica should be carried out to perform a reliable environmental risk assessment leading to propose recommendations to minimize the anthropic impact.

Nutrient over-enrichment in freshwater environments, together with the on-going climate change, favour the toxin-producing cyanobacteria bloom. Human health hazard may arise from drinking contaminated water. Additionally, cyanobacterial blooms affect other economic areas such as tourism, recreation, commercial fishery, water management and monitoring. Nowadays there is a scarcity of information on seasonal variations of cyanotoxins in various regions. Understanding of historical trends and seasonal variation patters is a foundation for forecasting and will help to develop effective water management strategies. This review gives an overview of cyanotoxins' analysis and levels in freshwater environments with particular emphasis on seasonal variations in Europe. Recent analytical approaches are discussed and the seasonal patterns for three major European climate zones (Mediterranean, continental, and Atlantic) were distinguished. Additionally, data from multi-year studies showed a tendency of increasing cyanotoxins' levels.

Marine phytoplankton, such as diatoms, are responsible for a considerable part of carbon fixation and form the basis of the marine food web. However, different factors, such as eutrophication, can affect their population growth and induce the production of toxins. During the last few years, the presence of domoic acid (DA) has increased worldwide in coastal areas. Its toxic properties and capacity to bioaccumulate through the food chain have reinforced the need for developing monitoring strategies to ensure the safety and quality of marine resources. In this work, a highly sensitive analytical method has been developed to be used as an early detection and quantification tool for DA in seawater. The method is based on a sample pre-treatment step by solid-phase extraction (SPE) and an instrumental analysis by hydrophilic interaction liquid chromatography coupled with high-resolution mass spectrometry (HILIC-HRMS). The method has been validated, showing good results in terms of sensitivity and repeatability. Limits of detection and quantification were 0.25 and 0.75 ng L−1 respectively, and acceptable recovery was in the range of 48–69%. Then, the method was applied to study a real scenario in the Ebro Delta where mariculture activities are relevant for the economy of the area. A total of 34 samples were collected in different campaigns during three seasons covering the two main delta bays (Alfacs and Fangar) and four lagoons (La Tancada, Illa de Buda, l'Encanyissada and Canal Vell). 65% of the samples had concentrations of DA at the ng L−1 level, ranging from 0.90 to 69.6 ng L−1. The highest levels were found in samples from Alfacs bay and the summer campaign. In the case of the lagoons, DA was detected only in La Tancada at 8.78 ng L−1 in the winter campaign. This study proves the prevalence of DA in highly eutrophic areas, during all seasons, often at trace level concentrations.

The so-called marine litter, and in particular microplastics (MPs) and nanoplastics (NPs), are ubiquitously distributed and recognised as an emerging risk for the environment and human health. It is known that marine environments are one of the most impacted areas and among them; coastal zones are the most contaminated ones. They are subjected to population pressure, tourism, harbours, desalination plants, marine traffic and fish farms. This review is focused on the Mediterranean Sea, currently considered one hot spot of microplastics pollution in the world, as a consequence of the high number of plastic marine litter generating activities and its characteristic morphology of semi-enclosed sea. MPs and NPs have been detected not only in surface water and water columns but also in sediments, deep seafloor, and biota including fish and seafood for human consumption. Because of this, different European legislation initiatives have been launched during the last years in order to prevent MPs and NPs contamination and to face derived problems. Finally, this review summarises the main problems and shortcomings associated to MPs and NPs analyses such as their identification and quantification or the necessity of standardised protocols.

The increasing frequency of episodes of harmful algal blooms of cyanobacterial origin is a risk to ecosystems and human health. The main human hazard may arise from drinking water supply and recreational water use. For this reason, efficient multiclass analytical methods are needed to assess the level of cyanotoxins in water reservoirs and tackle these problems. This work describes the development of a fast, sensitive, and robust analytical method for multiclass cyanotoxins determination based on dual solid-phase extraction (SPE) procedure using a polymeric cartridge, Oasis HLB (Waters Corporation, Milford, MA, USA), and a graphitized non-porous carbon cartridge, SupelcleanTM ENVI-CarbTM (Sigma-Aldrich, St. Louis, MO, USA), followed by ultra-high-performance liquid chromatography high-resolution mass spectrometry (SPE-UHPLC-HRMS). This method enabled the analysis of cylindrospermopsin, anatoxin-a, nodularin, and seven microcystins (MC-LR, MC-RR, MC-YR, MC-LA, MC-LY, MC-LW, MC-LF). The method limits of detection (MLOD) of the validated approach were between 4 and 150 pg/L. The analytical method was applied to assess the presence of the selected toxins in 21 samples collected in three natural water reservoirs in the Ter River in Catalonia (NE of Spain) used to produce drinking water for Barcelona city (Spain).